JP7116498B2 - Layered structure compound containing indium and arsenic, nanosheet and electric device using the same - Google Patents
Layered structure compound containing indium and arsenic, nanosheet and electric device using the same Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims description 72
- 239000002135 nanosheet Substances 0.000 title claims description 66
- 229910052785 arsenic Inorganic materials 0.000 title description 6
- 229910052738 indium Inorganic materials 0.000 title description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title description 4
- 239000000126 substance Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 12
- 238000005259 measurement Methods 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 28
- 239000000654 additive Substances 0.000 description 17
- 230000000996 additive effect Effects 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 9
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000004627 transmission electron microscopy Methods 0.000 description 7
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 6
- -1 transition metal chalcogen compounds Chemical class 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910000673 Indium arsenide Inorganic materials 0.000 description 4
- 238000004630 atomic force microscopy Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 4
- 238000000470 piezoresponse force microscopy Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 230000005621 ferroelectricity Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Description
本発明は、インジウムとヒ素を含む層状構造化合物とナノシートおよびこれを用いた電気素子に関し、より詳細には、アルカリ金属またはアルカリ土類金属を含み、多様な電気的特性を有するインジウムとヒ素を含む層状構造化合物とナノシートおよびこれを用いた電気素子に関する。 TECHNICAL FIELD The present invention relates to a layered structure compound and a nanosheet containing indium and arsenic and an electric device using the same, and more particularly, it contains indium and arsenic containing an alkali metal or an alkaline earth metal and having various electrical properties. The present invention relates to a layered structure compound, a nanosheet, and an electric device using the same.
層間（ｉｎｔｅｒｌａｙｅｒ）にファンデルワールス結合を通して連結される層状構造化合物は、多様な特性を示すことができ、これを物理的または化学的方法で分離することによって、厚さが数ナノメートルから数百ナノメートル水準の二次元（２Ｄ）ナノシートを製造できて、これに対する研究が活発である。 A layered structure compound that is connected between layers through van der Waals bonds can exhibit various properties, and can be separated by physical or chemical methods to achieve thicknesses ranging from several nanometers to hundreds of layers. Nanometer-level two-dimensional (2D) nanosheets can be produced, and research on this has been active.
特に、ナノシートのような低次元の素材は、従来のバルク素材が有しない画期的な新機能が期待され、従来素材を代替する次世代未来素材として可能性が非常に大きい。 In particular, low-dimensional materials such as nanosheets are expected to have epoch-making new functions that conventional bulk materials do not have, and have great potential as next-generation future materials to replace conventional materials.
しかしながら、二次元的結晶構造を有する層状構造化合物は、今まで黒鉛や遷移金属カルコゲン化合物等の物質に制限されていて、多様な組成の材料への展開にならない問題があった。 However, layered structure compounds having a two-dimensional crystal structure have hitherto been limited to substances such as graphite and transition metal chalcogen compounds, and there has been a problem that they cannot be developed into materials with various compositions.
一方、インジウムヒ素（Ｉｎｄｉｕｍ Ａｒｓｅｎｉｄｅ）は、化合物半導体物質であって、高電力高周波電気素子に広範囲に使用されているが、現在まで層状構造を有する三元系インジウムヒ素については知られていない。 On the other hand, indium arsenide, which is a compound semiconductor material, has been widely used in high-power, high-frequency electrical devices, but ternary indium arsenide having a layered structure has not been known so far.
層状構造からなる三元系インジウムヒ素化合物は、異なる結晶構造を有する従来のインジウムヒ素化合物においてさらに適用を多様化させることができると共に、従来適用されなかった新しい領域への適用も期待することができる。 A ternary indium arsenide compound having a layered structure can be applied to a wider variety of applications than conventional indium arsenide compounds having different crystal structures, and can be expected to be applied to new areas that have not been applied in the past. .
本発明は、インジウムとヒ素を含む層状構造化合物とこれを通して作製され得るナノシートおよび前記物質を含む電気素子を提供することを目的とする。 An object of the present invention is to provide a layered structure compound containing indium and arsenic, a nanosheet that can be produced through the compound, and an electric device containing the material.
前記のような目的を達成するために、本発明では、［化学式１］Ｎａ１－ｘＩｎｙＡｓｚ（０≦ｘ＜１．０、０．８≦ｙ≦１．２、１．２≦ｚ≦１．８）で表現される層状構造化合物を提供することができる。 In order to achieve the above objects, in the present invention, [chemical formula 1] Na 1-x In y As z (0≦x<1.0, 0.8≦y≦1.2, 1.2≦ It is possible to provide a layered structure compound represented by z≦1.8).
また、本発明では、前記［化学式１］Ｎａ１－ｘＩｎｙＡｓｚ（０≦ｘ＜１．０、０．８≦ｙ≦１．２、１．２≦ｚ≦１．８）で表現される組成物を含み、物理的または化学的剥離方法で作製されるナノシートを提供することができる。 In the present invention, the [Chemical Formula 1] Na 1-x In y As z (0≦x<1.0, 0.8≦y≦1.2, 1.2≦z≦1.8) Nanosheets can be provided that include the composition and are made by physical or chemical exfoliation methods.
また、本発明では、前記のような層状構造化合物またはナノシートを含む電気素子を提供することができる。 In addition, the present invention can provide an electric device including the layered structure compound or nanosheet as described above.
また、前記電気素子は、メモリスタであり得る。 Also, the electrical element may be a memristor.
本発明によって提供することができる層状構造化合物とナノシートは、多様な電気的特性を有することができ、これを通して新しい電気素子の開発が可能になる。 The layered structure compounds and nanosheets that can be provided by the present invention can have various electrical properties, which enables the development of new electrical devices.
以下、本発明の実施例について添付の図面を参考としてその構成および作用を説明することとする。下記で本発明を説明するに際して、関連した公知機能または構成に対する具体的な説明が本発明の要旨を不明にすることができると判断される場合には、その詳細な説明を省略する。また、任意の部分が或る構成要素を「含む」というとき、これは、特に反対になる記載がない限り、他の構成要素を除くものではなく、他の構成要素をさらに含むこができることを意味する。 The configuration and operation of embodiments of the present invention will now be described with reference to the accompanying drawings. In the following description of the present invention, if it is determined that a detailed description of related known functions or configurations may obscure the gist of the present invention, the detailed description thereof will be omitted. Also, when we say that any part "includes" a component, this does not exclude other components, but it can further include other components, unless specifically stated to the contrary. means.
本発明による層状構造化合物またはナノシートは、下記化学式１で表現され得る。
［化学式１］
Ｎａ１－ｘＩｎｙＡｓｚ（０≦ｘ＜１．０、０．８≦ｙ≦１．２、１．２≦ｚ≦１．８）
一般的に、ＩｎＡｓは、ジンクブレンド（Ｚｉｎｃ Ｂｌｅｎｄｅ）結晶構造であって、層状構造が現れることができず、したがって、これを剥離してナノシートを作製することも不可能であった。
A layered structure compound or nanosheet according to the present invention may be represented by Chemical Formula 1 below.
[Chemical Formula 1]
Na 1-x In y As z (0≦x<1.0, 0.8≦y≦1.2, 1.2≦z≦1.8)
Generally, InAs has a zinc blend crystal structure and cannot exhibit a layered structure, so it was impossible to exfoliate it to produce a nanosheet.
このような問題を克服するために、本発明の発明者らは、ＩｎｙＡｓｚに添加元素を添加することによって、ＩｎｙＡｓｚ層間に添加元素を位置させて、結果的に、ＩｎｙＡｓｚ層が続く層状構造化合物を製造することができると考えた。このために、発明者らは、計算を通して新しい組成と結晶構造を有する層状構造の物質を導き出し、その結果、従来報告されたことがない新しい組成である層状構造のＮａ２Ｉｎ２Ａｓ３を合成し、これを通して前記［化学式１］の組成を有する層状構造化合物を製造することができた。 In order to overcome such problems, the inventors of the present invention added an additive element to InyAsz to position the additive element between the InyAsz layers , resulting in Iny It was believed that a layered structure compound followed by an Asz layer could be produced. For this purpose, the inventors derived a layered structure material having a new composition and crystal structure through calculations, and as a result synthesized a layered structure Na 2 In 2 As 3 with a new composition that has never been reported before. Through this, a layered structure compound having the composition of [Chemical Formula 1] was produced.
［化学式１］の組成を有する層状構造の化合物は、ＩｎｙＡｓｚ層間にＮａが位置してＩｎｙＡｓｚ層をファンデルワールス結合を通して弱く結合させていて、これらＮａが位置する面は、この面に沿って容易に割れる劈開面（ｃｌｅａｖａｇｅ ｐｌａｎｅ）を成す。 In the layered structure compound having the composition of [Chemical Formula 1], Na is located between the In y As z layers to weakly bond the In y As z layers through van der Waals bonds, and the plane where these Na is located is It forms a cleavage plane along which it is easily broken.
一方、Ｎａ１－ｘＩｎｙＡｓｚ層状構造化合物またはナノシートにおいてＮａの組成は、上述した［化学式１］を基準として、ｘは、０であり得るが、上述したように、Ｎａ２Ｉｎ２Ａｓ３は、従来合成された事実が報告されたことがない新しい物質であって、［化学式１］においてｘは、０である場合に該当する。Ｎａの除去がなくてもＮａを含む面は、弱いファンデルワールス結合を成す劈開面であって、剥離が起こり得る。 On the other hand, in the composition of Na in the Na 1-x In y As z layered structure compound or nanosheet, based on [Chemical Formula 1] described above, x may be 0, but as described above, Na 2 In 2 As 3 is a new substance that has never been reported to be synthesized in the past, and corresponds to the case where x is 0 in [Chemical Formula 1]. Even without removal of Na, the planes containing Na are cleavage planes with weak van der Waals bonds and delamination can occur.
本発明による層状構造化合物は、上述したように、ＩｎｙＡｓｚ層間にＮａが位置してＩｎｙＡｓｚ層をファンデルワールス結合を通して弱く結合させていて、このような劈開面に沿ってＩｎｙＡｓｚ層に容易に物理的または化学的方法のうちいずれか一方または両方を通して剥離され得るが、このような剥離は、Ｎａが除去されるほどさらに容易に行われる。したがって、このような層状構造化合物から物理的または化学的剥離方法を通して容易にＩｎｙＡｓｚナノシートを作製することができ、ここで、ＩｎｙＡｓｚナノシートには、Ｎａが一部残留することもできる。 As described above, in the layered structure compound according to the present invention, Na is positioned between the In y As z layers to weakly bond the In y As z layers through van der Waals bonds, and In Although the y As z layer can be easily stripped through either or both of physical and chemical methods, such stripping becomes easier as Na is removed. Therefore, InyAsz nanosheets can be easily prepared from such a layered structure compound through a physical or chemical peeling method, and Na may partially remain in the InyAsz nanosheets . can.
添加元素であるＮａを持続的に除去すると、化合物においてＩｎｙＡｓｚ層間の距離が次第に広がって層間の結合力が弱まって、結局、層間の結合がなくなり、層間にクラック（ｃｒａｃｋ）を示すことができる。したがって、本発明で説明する層状構造化合物の層状構造は、繰り返される二次元のＩｎｙＡｓｚ層がＮａによりファンデルワールス結合で層間に結合がなされた場合だけでなく、ＩｎｙＡｓｚ層間の結合力が除去されて層間の距離が広がってクラックを示す場合も含む。このようにＮａが除去されて、層間の結合が弱くなることによって、ナノシートへの剥離もさらに容易に行われ得る。 When the additive element Na is continuously removed, the distance between the InyAsz layers in the compound gradually widens and the bonding strength between the layers weakens. Eventually, the bonding between the layers disappears and cracks appear between the layers. can be done. Therefore, the layered structure of the layered structure compound described in the present invention can be obtained not only when the repeated two-dimensional In y As z layers are bonded between the layers by van der Waals bonding with Na, but also when the In y As z layers It also includes the case where the bonding force is removed and the distance between the layers increases to show cracks. The removal of Na in this way weakens the bond between the layers, so that the nanosheet can be peeled off more easily.
このような層状構造化合物から剥離されて作製されるナノシートは、ＩｎｙＡｓｚ単一層であってもよいが、複数の層が重なって作製されることもできるので、数百ｎｍの厚さであってもよい。一般的に、ナノシートは、横方向の幅に対して厚さが一定水準以下である場合にのみ、二次元的な形状による異方性を示すことができるが、このために、ナノシートの幅Ｌに対する厚さｄの比ｄ／Ｌは、０．１以下であることが好ましい。本発明によって作製されるナノシートの幅は、５μｍ以上であることも可能なので、ナノシートの厚さは、５００ｎｍ以下であることが好ましい。ここで、ＩｎｙＡｓｚナノシートには、Ｎａが一部残留することもできる。 A nanosheet produced by exfoliation from such a layered structure compound may be a single In y As z layer, but it can also be produced by stacking a plurality of layers. It can be. In general, a nanosheet can exhibit anisotropy due to its two-dimensional shape only when the thickness is less than a certain level with respect to the width in the lateral direction. The ratio d/L of the thickness d to the thickness is preferably 0.1 or less. Since the width of the nanosheets produced by the present invention can be 5 μm or more, the thickness of the nanosheets is preferably 500 nm or less. Here, Na may partially remain in the InyAsz nanosheets .
このように本発明によるナノシートは、層状構造化合物から物理的または化学的方法で剥離されるシートを意味し、ＩｎｙＡｓｚ層が単一層である場合だけでなく、複数の層からなる場合も含む。 Thus, the nanosheet according to the present invention means a sheet that is physically or chemically exfoliated from a layered structure compound, and not only when the InyAsz layer is a single layer but also when it is composed of multiple layers. include.
このような層状構造化合物とナノシートの例に対する概念図は、図１に示したが、ＮａＩｎｙＡｓｚのＩｎｙＡｓｚ層１０の間に添加元素であるＮａ１１が位置してＩｎｙＡｓｚ層１０間に結合を維持することを示しており、ここで、Ｎａ１１が除去されてＮａ１－ｘＩｎｙＡｓｚになってＩｎｙＡｓｚ層１０間の結合が弱くなり、これを物理的または化学的に容易に剥離することができて、最終的にＩｎｙＡｓｚナノシート２０に作製されることを示す。このように作製されるナノシートには、依然としてＮａ１１が一部含まれ得る。
したがって、剥離が容易であると同時に、Ｎａの過度な除去による層状構造の崩壊または結晶構造の変化がないように、ｘは、０．１≦ｘ≦０．９であり得る。ここで、層状構造化合物の結晶構造は、空間群がＰ２１／ｃであり得る。このようなｘの範囲を有する層状構造化合物から剥離されるナノシートも、同一に、ｘは、０．１≦ｘ≦０．９であり得る。
A conceptual diagram of an example of such a layered structure compound and nanosheets is shown in FIG . 10, where
Therefore, x can be 0.1≦x≦0.9 so that peeling is easy and at the same time there is no collapse of the layered structure or change in the crystal structure due to excessive removal of Na. Here, the crystal structure of the layered structure compound may have a space group of P2 1 /c. A nanosheet exfoliated from a layered structure compound having such a range of x may also have x of 0.1≦x≦0.9.
また、Ｎａ１－ｘＩｎｙＡｓｚ層状構造化合物またはナノシートにおいて残留するＮａは、上述した［化学式１］を基準として、ｘは、０．３≦ｘ≦０．８の範囲であり得る。 In addition, in the Na 1-x In y As z layered structure compound or Na remaining in the nanosheet, x may be in the range of 0.3≦x≦0.8 based on [Chemical Formula 1] described above.
添加元素であるＮａが一部除去され、一定量は残留する層状構造化合物は、層間で残留する添加元素であるＮａが移動可能になって、これを通して多様な電気的特性を示すことができる。したがって、Ｎａ１－ｘＩｎｙＡｓｚ化合物において添加元素は、一定分率以上が除去され、一部は残ることが好ましい。このためのｘの範囲は、０．３≦ｘ≦０．８の範囲であり得る。 In the layered structure compound in which the additive element Na is partially removed and a certain amount remains, the remaining additive element Na can migrate between layers, and through this, various electrical properties can be exhibited. Therefore, it is preferable that a certain fraction or more of the additional element is removed from the Na 1-x In y As z compound, and a part of the added element remains. The range of x for this may be in the range 0.3≦x≦0.8.
［化学式１］においてｙは、０．８≦ｙ≦１．２であり、ｚは、１．２≦ｚ≦１．８の範囲であり得るが、初めて作られたＮａ２Ｉｎ２Ａｓ３においても、欠陥によってｙおよびｚは、小幅変動がありえ、Ｎａが除去されて除去工程中にＩｎとＡｓの比率も少しずつ変化することができるので、Ｎａ１－ｘＩｎｙＡｓｚにおいてｙとｚの値が定められたＮａの含量に対して結晶構造を変化させない範囲で変動することができる。 In [Formula 1], y is 0.8≦y≦1.2, and z can be in the range of 1.2≦z≦1.8, but in the first made Na 2 In 2 As 3 Also, y and z can vary slightly depending on the defect, and the ratio of In to As can also change slightly during the removal process as Na is removed, so y and z in Na 1−x In y As z can be varied within a range that does not change the crystal structure for a given Na content.
一方、添加元素の除去は、硝酸や塩酸のような強酸を用いることができるが、このような強酸を通して添加元素が除去されて強酸に含まれる水素イオンが添加元素が除去されたサイトに置換されて結合されて、水素が含まれる層状構造化合物とこれを通したナノシートを提供することができる。 On the other hand, the additive element can be removed by using a strong acid such as nitric acid or hydrochloric acid. The additive element is removed through such a strong acid, and the hydrogen ions contained in the strong acid are replaced with the site where the additive element is removed. It is possible to provide a layered structure compound containing hydrogen and a nanosheet therethrough.
このように水素イオンが含まれる層状構造化合物またはナノシートは、下記［化学式２］で表現され得る。
［化学式２］
Ｎａ１－ｘＨｎＩｎｙＡｓｚ
（０≦ｘ＜１．０、０．８≦ｙ≦１．２、１．２≦ｚ≦１．８、０＜ｎ≦ｘ）
ここで、水素イオンは、添加元素であるＮａを代替することによって除去されるＮａの量以下で追加される。
Such a layered structure compound or nanosheet containing hydrogen ions can be represented by the following [chemical formula 2].
[Chemical Formula 2]
Na1 - xHnInyAsz _
(0≤x<1.0, 0.8≤y≤1.2, 1.2≤z≤1.8, 0<n≤x)
Here, hydrogen ions are added in an amount equal to or less than the amount of Na removed by substituting Na as an additional element.
Ｎａが除去される量であるｘの範囲は、０．１≦ｘ≦０．９の範囲であり得、さらに好ましくは、０．３≦ｘ≦０．８の範囲であり得る。上述したように、添加元素が一部除去され、一部は残留すると、初期層状構造化合物であるＮａＩｎｙＡｓｚの層状構造をそのまま維持しつつ、添加元素であるＮａが一部除去されることによって、層間の結合力が弱まって容易にＩｎｙＡｓｚ層に剥離され得、残留する添加元素によって多様な電気的特性を示すことができる。 The range of x, which is the amount of Na removed, may be in the range of 0.1≦x≦0.9, and more preferably in the range of 0.3≦x≦0.8. As described above, when the additive element is partially removed and partially remains, the additive element Na is partially removed while maintaining the layered structure of NaInyAsz , which is the initial layered structure compound. As a result, the bonding force between the layers is weakened, so that the InyAsz layer can be easily separated , and various electrical properties can be exhibited depending on the remaining additive elements.
また、前記ｎは、ｘと同じ値であり得るが、除去される添加元素だけ水素イオンが代替して層状構造化合物に含まれ得る。 In addition, n may be the same value as x, but hydrogen ions may be substituted for the additive element to be removed and included in the layered structure compound.
上述した層状構造化合物とナノシートは、分析結果、多様な特性を示すが、このような特性を以下で説明する。 The layered structure compounds and nanosheets described above exhibit various properties as a result of analysis, and such properties will be described below.
上述した層状構造化合物とナノシートは、ＣｕＫα線を使用したＸＲＤ測定においてＰ２１／ｃの空間群を有することができる。 The layered structure compounds and nanosheets described above can have a space group of P2 1 /c in XRD measurements using CuKα radiation.
一方、上述した層状構造化合物またはナノシートは、ＣｕＫα線を使用したＸＲＤ測定において２θ＝１１．９°± ０．５０°、１２．８°±０．５０°、１３．５°±０．５０°、１５．３°±０．５０°、２１．６°±０．５０°、２２．７°±０．５０°、２３．８°±０．５０°、２７．８°±０．５０°の位置にピークを有し、前記ピークは、最も大きい強度を有するピークに対して１％以上（好ましくは、３％以上、より好ましくは、５％以上）の強度を有するピークである、層状構造化合物またはナノシートであり得る。 On the other hand, the layered structure compound or nanosheet described above has 2θ = 11.9° ± 0.50°, 12.8° ± 0.50°, 13.5° ± 0.50° in XRD measurement using CuKα rays. , 15.3°±0.50°, 21.6°±0.50°, 22.7°±0.50°, 23.8°±0.50°, 27.8°±0.50° and the peak has an intensity of 1% or more (preferably 3% or more, more preferably 5% or more) with respect to the peak having the highest intensity. It can be a compound or a nanosheet.
一方、層状構造化合物またはナノシートから添加元素が除去されることによって、ＸＲＤ測定ピークにおいて微細な変化がありえるが、このような変化によってＣｕＫα線を使用したＸＲＤ測定において層状構造化合物の（００２）面に対するピーク強度に対する（１０２）面のピーク強度であるＩ（１０２）／Ｉ（００２）の値が０．４０以下であり得る。これは、層状構造化合物から添加元素が除去されることによって層間の距離が次第に広がって現れる現象であり、ナノシートに対しても同一である。 On the other hand, when the additive element is removed from the layered structure compound or nanosheet, there may be a slight change in the XRD measurement peak. A value of I (102) /I (002) , which is the peak intensity of the (102) plane relative to the peak intensity, may be 0.40 or less. This is a phenomenon in which the distance between layers gradually widens due to the removal of the additive element from the layered structure compound, and the same is true for nanosheets.
このような添加元素であるＮａが一部残留する状態である層状構造化合物とこれを通したナノシートは、残留するＮａによって多様な電気的特性を示すことができる。 The layered structure compound in which Na, which is an additive element, partially remains and the nanosheet through it can exhibit various electrical properties depending on the remaining Na.
上述したような層状構造化合物またはナノシートは、固有の層状構造と残留する添加元素によって多様な電気的特性を示すことができる。 A layered structure compound or nanosheet as described above can exhibit various electrical properties depending on the inherent layered structure and residual additive elements.
まず、本発明による層状構造化合物またはナノシートは、強誘電類似（ｆｅｒｒｏｅｌｅｃｔｒｉｃ－ｌｉｋｅ）特性を示す。 First, the layered structure compounds or nanosheets according to the present invention exhibit ferroelectric-like properties.
強誘電特性は、一般的にペロブスカイト構造のＢａＴｉＯ３のような非対称構造の酸化物に現れる特性であって、中心に位置するＢａの位置の変化によって強誘電特性が現れる。 Ferroelectricity is a characteristic that generally appears in oxides with an asymmetric structure such as perovskite BaTiO 3 , and the ferroelectricity appears depending on the position of Ba located in the center.
しかしながら、本発明による層状構造化合物またはナノシートは、このような非対称構造を有しないが、それにもかかわらず、強誘電類似特性を示す。非対称構造でないにもかかわらず、強誘電類似特性を示す理由は、残留する添加元素の位置が外部電界によって移動するのに伴ったものと考えられる。 However, the layered structure compounds or nanosheets according to the invention do not have such an asymmetric structure, but nonetheless exhibit ferroelectric-like properties. The reason why the ferroelectric-like properties are exhibited in spite of the fact that the structure is not asymmetric is thought to be due to the movement of the position of the remaining additive element due to the external electric field.
このような本発明による層状構造化合物またはナノシートの強誘電類似特性を通して多様な電気素子に適用が可能になる。 Such ferroelectric-like properties of the layered structure compound or nanosheet according to the present invention can be applied to various electric devices.
また、本発明による層状構造化合物またはナノシートは、抵抗スイッチング特性を示す。 Also, the layered structure compounds or nanosheets according to the present invention exhibit resistive switching properties.
或る物質が抵抗スイッチング特性を有すると、その物質に印加する電圧によって線形的に電流が増加するのではなく、初期電圧を印加するときには、物質が高抵抗状態を維持して電流の増加が微小であるが、一定の臨界点に到達すると、低抵抗状態に変わって急激に電流が増加する。 When a material has resistance-switching properties, the current does not increase linearly with the voltage applied to the material, but when an initial voltage is applied, the material maintains a high resistance state and the current increase is very small. However, when it reaches a certain critical point, it changes to a low resistance state and the current increases abruptly.
このような抵抗スイッチング特性は、一般的に酸化物に現れる特徴であって、最近には、このような特性を用いてフラッシュメモリのように情報の保存が可能なメモリスタ（ｍｅｍｒｉｓｔｏｒ）のようなメモリー素子の開発が活発であり、本発明の層状構造化合物とナノシートは、抵抗スイッチング特性を活用してこのようなメモリスタのようなメモリー素子の開発に積極的に活用され得る。 Such a resistance switching characteristic is a characteristic that generally appears in oxides. Devices are being actively developed, and the layered structure compound and nanosheets of the present invention can be actively used in the development of memory devices such as memristors by utilizing their resistance switching properties.
［実施例］
１）層状Ｎａ２Ｉｎ２Ａｓ３合成
ＮａとＩｎ、Ａｓをモル比で２：２：３の割合で称量して混合した後、アルミナるつぼに投入した。その後、クォーツチューブに入れ、二重密封して、外部空気を遮断した。この過程は、アルゴン雰囲気のグローブボックスで進めた。その後、ボックス炉で１，０００℃に昇温し、１２時間維持し、５℃／ｈの減温速度で５００℃まで冷却後、５００℃の温度で１００時間維持した後、常温に冷却して、Ｎａ２Ｉｎ２Ａｓ３サンプルを得ることができた。
[Example]
1) Synthesis of layered Na 2 In 2 As 3 Na, In, and As were weighed and mixed in a molar ratio of 2:2:3, and then charged into an alumina crucible. It was then placed in a quartz tube and double-sealed to block outside air. This process proceeded in an argon atmosphere glove box. After that, the temperature was raised to 1,000°C in a box furnace, maintained for 12 hours, cooled to 500°C at a temperature reduction rate of 5°C/h, maintained at 500°C for 100 hours, and then cooled to room temperature. , Na 2 In 2 As 3 samples could be obtained.
２）Ｎａの除去
エタノールで希釈された０．２５ＭのＨＣｌ溶液で時間別に反応させて、層状Ｎａ２Ｉｎ２Ａｓ３からＮａを除去した。その結果は、下記の表に示した。表１で、残留Ｎａは、ＥＤＳ分析を通して得られた結果を示す。
2) Removal of Na Na was removed from the layered Na 2 In 2 As 3 by reacting with 0.25 M HCl solution diluted with ethanol for different time periods. The results are shown in the table below. In Table 1, residual Na indicates the results obtained through EDS analysis.
３）ナノシート化工程
前記表１のように製造されたサンプルに対してエタノールで超音波を照射した後、テープを用いて剥離されたナノシートを製造した。
3) Process of Forming a Nanosheet A nanosheet was produced by irradiating ultrasonic waves with ethanol to the samples prepared as shown in Table 1, and peeling them off using a tape.
発明者らは、従来報告されたことがない新しいＮａ２Ｉｎ２Ａｓ３化合物に対してＶＡＳＰ（Ｖｉｅｎｎａ Ａｂ ｉｎｉｔｉｏ Ｓｉｍｕｌａｔｉｏｎ Ｐａｃｋａｇｅ）を用いた計算を通して層状構造を予測し、予測結果は、知られたＮａ２Ａｌ２Ａｓ３、Ｎａ２Ｇａ２Ａｓ３と同様に、Ｐ２１／ｃの構造を有することができることが分かった。 The inventors predicted a layered structure through calculation using VASP (Vienna Abinitio Simulation Package) for a new Na 2 In 2 As 3 compound that has never been reported before. 2 Al 2 As 3 , Na 2 Ga 2 As 3 , it was found that they could have a structure of P2 1 /c.
図２は、ＶＡＳＰを活用した計算を通して予測されたＮａ２Ｉｎ２Ａｓ３のＸＲＤ回折パターン（Ｎａ２Ｉｎ２Ａｓ３＿ｖａｓｐ）と上述した方法で合成されたサンプルＡ（Ｎａ２Ｉｎ２Ａｓ３＿ｓｙｎｔｈｅｓｉｓ）のＸＲＤ回折パターンを示す。計算されたデータによるピークと実際に合成された化合物であるサンプルＡに対するデータのピークを比較したとき、（００２）、（２００）、（１０２）、（１１１）、（２１２）、（３０２）、（３１１）、（１１４）の面が検出されることを確認した。前記面の２θ角は、それぞれ１１．９°、１２．８°、１３．５°、１５．３°、２１．６°、２２．７°、２３．８°、２７．８°であった。 FIG. 2 shows the XRD diffraction pattern of Na 2 In 2 As 3 (Na 2 In 2 As 3 _vasp ) predicted through calculation using VASP and sample A (Na 2 In 2 As 3 _synthesis ) shows the XRD diffraction pattern. When comparing the calculated data peaks with the data peaks for Sample A, which is the actually synthesized compound, (002), (200), (102), (111), (212), (302), It was confirmed that the (311) and (114) planes were detected. The 2θ angles of the faces were 11.9°, 12.8°, 13.5°, 15.3°, 21.6°, 22.7°, 23.8° and 27.8°, respectively. .
図３は、合成されたサンプルＡに対するＳＥＭ（Ｓｃａｎｎｉｎｇ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐy）イメージおよびＥＤＳ（Ｅｎｅｒｇｙ Ｄｉｓｐｅｒｓｉｖｅ Ｓｐｅｃｔｒｏｓｃｏｐｙ）分析結果を示す。ＥＤＳ結果を通して合成したサンプルＡは、Ｎａ、Ｉｎ、Ａｓで構成されていることが分かった。 FIG. 3 shows an SEM (Scanning Electron Microscopy) image and an EDS (Energy Dispersive Spectroscopy) analysis result of the synthesized sample A. FIG. Sample A synthesized through EDS results was found to consist of Na, In, As.
図４は、サンプルＡに対するＴＥＭ（Ｔｒａｎｓｍｉｓｓｉｏｎ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐy）分析結果を示す。サンプルＡに対してＴＥＭによるＳＡＥＤ（Ｓｅｌｅｃｔｅｄ Ａｒｅａ Ｄｉｆｆｒａｃｔｉｏｎ）分析結果、（００１）方向にＰ２１／ｃの空間群が現れるパターンが測定され、それぞれの（１００）、（０２０）、（１２０）面間の距離は、計算値と測定値が類似していることが示された。 FIG. 4 shows the TEM (Transmission Electron Microscopy) analysis results for sample A. FIG. As a result of SAED (Selected Area Diffraction) analysis by TEM for sample A, a pattern in which a space group of P2 1 / c appears in the (001) direction was measured, and each (100), (020), (120) plane It was shown that the calculated and measured distances are similar.
図５は、Ｎａ２Ｉｎ２Ａｓ３の構造を示す模式図とサンプルＡに対するＳＴＥＭ（Ｓｃａｎｎｉｎｇ Ｔｒａｎｓｍｉｓｓｉｏｎ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐy）分析結果を示す。ＳＴＥＭ分析結果、合成されたサンプルＡは、Ｐ２１／ｃの空間群を有することを確認した。 FIG. 5 shows a schematic diagram showing the structure of Na 2 In 2 As 3 and STEM (Scanning Transmission Electron Microscopy) analysis results for sample A. As shown in FIG. As a result of STEM analysis, it was confirmed that the synthesized sample A has a space group of P2 1 /c.
このように図２～図５での結果を通して、合成されたサンプルＡは、Ｐ２１／ｃの空間群を有する新しい組成と結晶構造を有する層状構造物質であるＮａ２Ｉｎ２Ａｓ３であることを確認することができた。 Thus, through the results in FIGS. 2 to 5, the synthesized sample A is Na 2 In 2 As 3 , a layered structure material having a new composition and crystal structure with a space group of P2 1 /c. was able to confirm.
図６は、Ｎａ除去によるＸＲＤピークの変化を示す。Ｎａが除去されないサンプルＡでは、（００２）面の面間間隔は、７．４２Åであり、ここで、Ｎａが除去されるほど面間間隔は次第に広がって７．４７Åまで増加することが認められた。このような面間間隔の変化によってＸＲＤピークの変化も現れるが、Ｎａの除去によって（００２）面のピークに対して（１０２）面のピークの大きさが次第に減少することが分かった。したがって、Ｉ（１０２）／Ｉ（００２）の値は、サンプルＡでは０．４６であり、サンプルＢでは、０．１３、サンプルＤでは、０．０９まで減少した。また、Ｎａ除去後にも、ＸＲＤピークを比較してみたとき、（００２）、（１０２）面のピークが同一に現れることから見て、Ｐ２１／ｃの空間群を有する結晶構造が維持されることが分かった。 FIG. 6 shows changes in XRD peaks due to Na removal. In Sample A, where Na was not removed, the interplanar spacing of the (002) planes was 7.42 Å, where it was observed that the interplanar spacing gradually increased to 7.47 Å as more Na was removed. rice field. It was found that the change in the interplanar spacing causes the XRD peak to change, but the removal of Na gradually reduces the magnitude of the peak of the (102) plane relative to that of the (002) plane. Therefore, the value of I (102) /I (002) was 0.46 for sample A, decreased to 0.13 for sample B, and 0.09 for sample D. In addition, even after removing Na, when the XRD peaks are compared, the peaks of the (002) and (102) planes appear the same, indicating that the crystal structure having the P2 1 /c space group is maintained. I found out.
図７は、サンプルＡからＮａを除去してサンプルＣになり、これからテープを用いて剥離されて作製されたナノシートを示す。サンプルＡは、層間の劈開面が観察されるが、サンプルＣでは、Ｎａが除去されることによって、層間隔が広がってクラックが形成されたことが認められた。 FIG. 7 shows a nanosheet produced by removing Na from sample A to form sample C, which was then peeled off using a tape. In sample A, cleavage planes between layers were observed, but in sample C, it was found that the removal of Na widened the gap between layers and formed cracks.
図８は、このようにサンプルＣから剥離されて作製されたナノシートに対するＡＦＭ（Ａｔｏｍｉｃ Ｆｏｒｃｅ Ｍｉｃｒｏｓｃｏｐｙ）イメージおよびそれに応じたラインプロファイル（ｌｉｎｅ ｐｒｏｆｉｌｅ）を示す。１０～３０ｎｍの厚さを有するナノシートに剥離されたことを確認することができた。 FIG. 8 shows an AFM (Atomic Force Microscopy) image of the nanosheet prepared by exfoliating from Sample C and a corresponding line profile. It was confirmed that the nanosheets were exfoliated with a thickness of 10-30 nm.
図９は、サンプルＤに対するＳＴＥＭ（Ｓｃａｎｎｉｎｇ Ｔｒａｎｓｍｉｓｓｉｏｎ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐy）分析結果である。このデータからＮａが一部除去されたことが分かり、除去された後にも結晶構造の変化がないことが分かった。
図１０は、サンプルＥに対するＴＥＭ分析結果である。Ｎａが過度に除去されることによって、非晶質構造が現れることが分かった。
FIG. 9 shows STEM (Scanning Transmission Electron Microscopy) analysis results for sample D. FIG. From this data, it was found that Na was partially removed, and it was found that there was no change in the crystal structure after removal.
10 is a TEM analysis result for sample E. FIG. It was found that an amorphous structure appeared due to excessive removal of Na.
サンプルＣから剥離されたナノシートに対してＰＦＭ（Ｐｉｅｚｏｒｅｓｐｏｎｓｅ Ｆｏｒｃｅ Ｍｉｃｒｏｓｃｏｐｙ）を通して強誘電特性を測定し、それによる結果を図１１に示した。実際に強誘電類似特性を有していることを確認することができた。 Ferroelectric properties of the nanosheet exfoliated from Sample C were measured through PFM (Piezoresponse Force Microscopy), and the results are shown in FIG. It was confirmed that it actually has ferroelectric-like characteristics.
また、サンプルＣから剥離されたナノシートに対して電圧に応じた電流変化を測定し、その結果を図１２に示した。 Also, the change in current according to the voltage was measured for the nanosheet peeled from Sample C, and the results are shown in FIG.
初期電圧では、高抵抗状態１を維持して低い電流の流れを示すが、一定電圧以上になると、低抵抗状態２になって急激に電流が増加することを示し、反対電極方向でも同じ特性が現れることが認められて、抵抗スイッチング特性を示すことが分かった。
At the initial voltage, the
このような抵抗スイッチング特性を利用すると、最近ニューロモーフィックメモリー素子として開発が活発に行われているメモリスタ素子に適用することができることが分かった。 It has been found that using such a resistance switching characteristic can be applied to a memristor device, which is being actively developed as a neuromorphic memory device.
Claims (24)
［化学式１］
Ｎａ１－ｘＩｎｙＡｓｚ
（０≦ｘ≦０．９、０．８≦ｙ≦１．２、１．２≦ｚ≦１．８） A layered structure compound represented by the following chemical formula 1.
[Chemical Formula 1]
Na 1-x In y Asz
( 0≤x≤0.9 , 0.8≤y≤1.2, 1.2≤z≤1.8)
［化学式１］
Ｎａ１－ｘＩｎｙＡｓｚ
（０≦ｘ≦０．９、０．８≦ｙ≦１．２、１．２≦ｚ≦１．８） A nanosheet comprising a composition represented by Chemical Formula 1 below.
[Chemical Formula 1]
Na 1-x In y Asz
( 0≤x≤0.9 , 0.8≤y≤1.2, 1.2≤z≤1.8)
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